Richard M. Laine University of Michigan
Clement Sanchez Universite Pierre et Marie Curie
Christophe Barbe Ceramisphere, ANSTO
Ulrich Schubert Vienna University of Technology
S2: Mesoporous Materials I
Tuesday AM, April 10, 2007
Room 2004 (Moscone West)
9:15 AM - **S5.1
Mesoporous Hybrid Thin Films: Building Blocks for Complex Materials with Spatial Organization.
Galo Soler-Illia 1 2 , Paula Angelome 1 , M. Cecilia Fuertes 1 , Alejandro Wolosiuk 1 , Sara Bilmes 2 , Javier Lopez-Alcaraz 3 , Hernan Miguez 3 Show Abstract
1 Unidad de Actividad Química, Comisión Nacional de Energía Atómica, San Martín, Buenos Aires, Argentina, 2 INQUIMAE-DQIAQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Buenos Aires Argentina, 3 Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Científicas, Sevilla Spain
9:45 AM - **S5.2
Inorganic and Hybrid Thin Layers with Specific Designs.
Vincent Rouessac 1 , Andre Ayral 1 Show Abstract
1 Institut Européen des Membranes UMR n° 5635 CNRS-ENSCM-UM2, CC047, Université Montpellier 2, F34095 Montpellier cedex 5 France
10:15 AM - **S5.3
Dynamic Supramolecular Hybrid Membranes
Mihai Barboiu 1 Show Abstract
1 Adaptative Supramolecular Nanosystems, Institut Europeen des Membranes, Montpellier France
The chemistry of membrane transport systems of interest for molecular information transfer has been extensively developed during the last twenty years. Our interest focus on hybrid solid membranes in which the molecular recognition-driven transport function could be ensured by a dynamic incorporation of specific organic receptors covalently and non-covalently linked in a dense and mesoporous siloxane inorganic matrix. Of particular interest is the potential ability of such solid membranes to combine functional properties such as solute molecular recognition, generation by self-assembling of the directional conduction pathways and target-constitutional evolution at the supramolecular level.From the mechanistic point of view, we use heteroditopic carriers which self-assemble in functional aggregates which would present combined (hybrid) intermediate features between the former carrier-monomers and the resulted pseudo-channel-forming superstructures. Thus, we therefore studied the membrane transport properties of such supramolecular systems resulted by the dynamic self-assembly of the hydrogen-bonded urea-crown ethers or bioorganic molecules in solid dense or mesoporous hybrid membranes. The crown-ether self-organized systems can be “frozen” in a polymeric hybrid matrix, opening the door to the design of a novel class of organic-inorganic nanomembranes. New self-organized hybrid membrane materials have been prepared from heteropolysiloxane superstructures chemically fixed in a silica matrix by sol-gel process. They have been employed to design the solid dense membranes, functioning as an ion-powered ATP pump.The selective recognition functions and self organization can be transferred inside regular mesoporous nanochannels. The MCM41-type mesostructured powders and membranes were used as hydrophobic or hydrophilic host matrix for physically or chemically entrapped 15-crown-5 and 18-crown-6 self-organized receptors. The combined features of structural adaptation in a specific hybrid nanospace and of dynamic supramolecular selection process make the membranes presented here of general interest for the development of a specific approach toward nanomembranes of increasing constitutional selectivity. 1.Barboiu, M.; Guizard, C.; Hovnanian, N.; Palmeri, J.; Reibel, C.; Luca, C.; Cot, L. J. Membrane Sci. 2000, 172, 91-103. 2.Barboiu, M.; Guizard, C.; Hovnanian, N.; Cot, L. Sep. Tech. Pur., 2001, 25, 211-218. 3.Barboiu, M.; Vaughan, G.; van der Lee A., Org. Lett., 2003, 5 (17), 3073-3076. 4.Barboiu, M., J. Incl. Phenom. Mol Rec. 2004, 49 133-137. 5.Barboiu, M.; Cerneaux, S.; Vaughan, G.; van der Lee, A.. J. Am. Chem. Soc., 2004, 126, 3545-3550. 6. Cazacu,A.; Tong,C.; van der Lee A., Fyles, T.; Barboiu,M. J. Am. Chem. Soc. 2006, 128, 9541-9548.
10:45 AM - S2:Meso 1
11:15 AM - S5.4
Hybrid Organic-Inorganic Membranes with Long-Term Stability for Pervaporation.
Hessel Castricum 1 2 , Ashima Sah 1 , Jaap Vente 3 , Johan ten Elshof 1 Show Abstract
1 Inorganic Materials Science, MESA+ Institute for Nanotechnology, Universiteit Twente, Enschede Netherlands, 2 Van ‘t Hoff Institute for Molecular Sciences, Universiteit van Amsterdam, Amsterdam Netherlands, 3 Molecular Separation Technology, Energy research Centre of the Netherlands, Petten Netherlands
Molecular separation processes are responsible for an estimated 40% of the total energy consumption in the (petro)chemical industry worldwide, i.e. more than 10 billion barrels of oil equivalent per year. These separations are currently performed using (cryogenic) distillation or adsorption-based techniques. The energy efficiency of these techniques is in general as low as 10%. Molecular separations based on membrane technology are generally accepted as one of the possible alternatives thanks to their inherently low energy consumption. Thermal, mechanical and chemical (solvent) stability are poor for polymeric membranes, while improvement of the hydrothermal stability is the main challenge for ceramic membranes in order to be able to work under humid conditions. As a consequence, the state-of-the-art membranes, i.e. PVA-based materials and methylated silca, have a application temperatures below ~100°C with minor associated benefit. In order to be cost-efficient, a membrane should be able to function at temperatures up to at least 150°C for several years.Mechanical stresses built-up during the sol-gel preparation of silica-based membranes are responsible for promoting hydrolysis of siloxane network bonds, resulting in the destruction of the microstructure in water. We have succeeded in preparing an organic/inorganic network material with a truly hybrid character by the application of a bis-silyl precursor. While this precursor suffers from extensive autocondensation and di-/trimerisation, resulting in the formation of non-reactive complexes and the development of a dense solid structure, we have been able to successfully suppress this mechanism by mixing with silane co-reactants and ensuring very gradual hydrolysis and condensation. This resulted in a microporous structure with a high organic fraction. Through the careful control over the coating procedure, a supported defect-free thin layer (< 100 nm) with a high hydrothermal stability has been obtained. The organic linking groups provide a ‘core network’ of unhydrolysable moieties and provide flexibility, which limits strain in the siloxane bonds. This leads to a high stability in water-containing media at increased temperatures. Moreover, they promote stress relaxation of the thin coated film during the preparation procedure and perseverance of the structure against thermal and pressure gradients. Consequently, the material is highly resistant to cracking. As a result, a membrane has been produced that can be applied in the dehydration of n-butanol up to at least 150°C for more than one year, bringing industrial application within close reach.
11:30 AM - S5.5
Nanoparticle Assembly of Ordered Multicomponent Mesostructured Metal Oxides via a Versatile Sol-gel Process
Jie Fan 1 , Shannon Boettcher 1 , Galen Stucky 1 Show Abstract
1 Chemistry and Biochemistry, University of California, Santa Barbara, California, United States
Multi-component metal oxides have attracted attention for their potential use in electronic, (photo)catalytic, photovoltaic, and energy storage applications. The ability to simultaneously control the nanoscale structure and composition of such materials using simple and inexpensive routes is important for that potential to be realized. Here we introduce a simple and widely-applicable methodology for the synthesis of multicomponent mesostructured metal oxides (MMMOs) from the combination of inexpensive and commercially available polymers with metal alkoxides solubilized in a sol-gel solution consisting of acetic acid, hydrochloric acid and ethanol (AcHE). MMMOs obtained utilizing the AcHE system have tunable pore structures, a high degree homogeneity, and in certain cases thermal stability above 1000 oC. The ability to easily process these diverse MMMOs in the form of thin films, free standing membranes, and monoliths provides distinct advantages over previously reported MMO synthesis procedures—especially when large quantities of material are required, for instance, in heterogeneous catalyst development. Most importantly, we demonstrate that using this method, the diverse condensation kinetics of a variety of metal oxide materials can be homogenized—which allows for the fabrication of complicated and novel MMMO compositions (e.g. rare earth and transition metal oxides). The development of such simple and widely-applicable methodologies are extremely important for the practical implementation of porous metal oxides.
11:45 AM - S5.6
Inorganic/organic Polymer Films Formed via Plasma Enhanced Chemical Vapor Deposition.
Jesse Enlow 1 , Hao Jiang 1 , Kurt Eyink 1 , Mark Foster 2 , Somesh Peri 2 , John Grant 3 , Timothy Bunning 1 Show Abstract
1 , Air Force Research Laboratory, WpAFB, Ohio, United States, 2 , U. Akron, Akron, Ohio, United States, 3 , UDRI, Dayton, Ohio, United States
12:00 PM - **S5.7
Mesoporous Carbon Nitrides: a First Step towards Metal-Free Heterogeneous Catalysis.
Frederic Goettmann 1 , Anna Fisher 1 , Philippe Makovski 1 , Markus Antonietti 1 , Arne Thomas 1 Show Abstract
1 Colloid Chemistry, Max-Planck-Institut for Colloids and Interfaces, Potsdam Germany
The use of transition metals in catalysis is considered as the great chemical success story of the XXth century. Nevertheless, increasing noble metals prices and evidence of large amounts of metals in soil or polar ices rose concerns about the sustainability of industrial process relying on such metal. Therefore, homogeneous organic catalysis attracted increased attention in recent years.[2; 3] An additional step towards more sustainable industrial process would be the development of a whole class of heterogeneous organic catalysts. Besides graphite, carbon nitrides are a very promising class of material for this purpose. Graphitic C3N4 is easily available through thermal condensation of cyanamide. This C3N4 material features graphene like layers of tris-s-triazine units and is especially interesting for its electronic properties. In order to investigate the potential catalytic performances of this material, increased surface was obtained by a nanocasting approach relying on the use of silica nanospheres as a hard template. The resulting powders exhibited surface area up to 400 m2.g-1. This mesoporous graphitic C3N4 (mpgC3N4) was then successfully used as a catalyst in various reactions:- The Friedel-Crafst acylation of benzene relying on an activation of the aromatic ring through electron transfer from the solid to the ring.[6; 7]- The cyclotrimerization of substituted nitriles and alkynes.- The activation of CO2 and benzene to form Phenol and CO.- The synthesis of various organic carbonates starting with CO and the corresponding alcohols.These very promising results drove us to investigate the synthesis and properties of other carbon nitrides like C3N3, N=N double bonds doped graphite… W. A. Herrmann and B. Cornils, Angew. Chem.-Int. Edit. Engl. 36, 1997, 1049-1067. P. I. Dalko and L. Moisan, Angew. Chem.-Int. Edit. 43, 2004, 5138-5175. B. List, Accounts Chem. Res. 37, 2004, 548-557. D. S. Su, N. Maksimova, J. J. Delgado, N. Keller, G. Mestl, M. J. Ledoux and R. Schlogl, Catal. Today 102, 2005, 110-114. B. Jurgens, E. Irran, J. Senker, P. Kroll, H. Muller and W. Schnick, J. Am. Chem. Soc. 125, 2003, 10288-10300. F. Goettmann, A. Fischer, M. Antonietti and A. Thomas, Angew. Chem. Int. Ed. 45, 2006, 4467 –4471. F. Goettmann, A. Fischer, M. Antonietti and A. Thomas, Chem. Commun.2006, DOI: 10.1039/b608532f. F. Goettmann, A. Fischer, M. Antonietti and A. Thomas, New. J. Chem.2006, Submitted. F. Goettmann, A. Thomas and M. Antonietti, Angew. Chem. Int. Ed.2006, accepted.
12:30 PM - **S5.8
From Polymeric to Particulate Inorganic Macrocellular Foams:Some Integrative Chemistry Synthetic Pathways
Florent Carn 1 , Renal Backov 1 Show Abstract
1 , CNRS-Universite Bordeaux-I, Pessac France
Designing new porous materials in a monolithic state with a framework involving hierarchical porous systems while tuning the macroscopic void spaces is an emerging area of technological interests dedicated toward several applications as for instance heterogeneous catalysis, separations, artificial bone structure, thermal and/or acoustic insulation, ion-exchange operation and so forth. Recently a new concept of “Integrative Chemistry” has been postulated and can be defined as a transversal tool box, ranging from chemistry, physical chemistry and biology, where researchers might find the entire ingredients to compose complex architectures (porous or not) in order to reach the desired specific function or polyfunctionalities. First we will discussed the syntheses of polymeric foams based on SiO2 , TiO2 scaffolds and the design of the macroporous networks while maintaining a good mesoporosity, as for instance a specific surface area of 400 m2.g-1 can be reached when generating Anatase titanium dioxide macrocellular foams. Secondly we will show how macrocellular foams might be generated playing with nano-building blocks where the nanoparticles intrinsic aspect ratio can be switched from one dimensional vanadium oxide ribbons, zirconium phosphate exfoliated sheets, and silica monodisperse spherical nanoparticles. In this later case, the as synthesized opal-like skeleton provide a tunable surface roughness by using different size of silica colloidal particles while the macropore morphology (i.e. pore wall thickness, pore wall length) can be tune by a continuous control over the foam’s liquid fraction and the gas bubble size during the mineralization process. Moreover open or closed pore structure can be reached upon the foam’s liquid fraction and the colloidal particle size involved during the foaming process. 1- R. Backov, Soft Matter, 2006, 2, 452.2- F. Carn, A. Colin, M.-F. Achard, H. Deleuze, R. Backov Adv. Mater., 2004, 6, 140.3- F. Carn, A. Colin, M.-F. Achard, H. Deleuze, C. Sanchez, R. Backov, Adv. Mater., 2005, 17, 62.4- F. Carn, M-F. Achard, O. Babot, H. Deleuze, S. Reculusa and R. Backov, J. Mater. Chem., 5- F. Carn, N. Steunou , A. Colin, J. Livage, R. Backov Chem. Mater. 2005, 17, 644. 6- F. Carn, A. Derré, W. Neri, O. Babot, H. Deleuze, R. Backov, New J. Chem., 2005, 29, 13467- F. Carn, P. Massé, S. Ravaine, H. Deleuze, C. Sanchez, B. Julian, D.R. Talham, R. Backov Langmuir, 2006, 22, 5469.
S4: Poster Session: Organic/Inorganic Materials I
Wednesday AM, April 11, 2007
Salon Level (Marriott)
9:00 PM - S4.1
Phase Separation in Alkoxy-Derived Silica System Containing Polyacrylamide
Kousuke Kawamoto 1 , Kazuki Nakanishi 1 , Teiichi Hanada 1 Show Abstract
1 Department of Chemistry, Graduated School of Sience, Kyoto University, Kyoto Japan
By inducing phase separation parallel to the sol-gel transition of alkoxy-derived silica systems, we can obtain gels having both co-continuous macropores and mesopores. The tendency of phase separation induced by polymerization of alkoxysilane can be controlled by the starting composition and reaction temperature. Relation between the parallel dynamics, formation of phase domains and sol-gel transition, determines the final morphologies frozen in the gel network. Tetramethoxysilane (TMOS) as a silica source, polyacrylamide (average MW=10,000) and aqueous nitric acid solution were mixed for hydrolysis, and kept closed at constant temperature. Polyacrylamide(PAAm), which exhibits a strong hydrogen-bonding interaction with silica, was used as a phase-separation inducer. Gels thus prepared were evaporation-dried after solvent exchange by ethanol or water/ethanol. Some of the dried gels were heat-treated. From limited starting compositions, we obtained silica gels having hierarchical macro/mesoporous structure. At higher PAAm concentrations, after vigorous ethanol washing, pores measured by the nitrogen adsorption distributed in significantly large pore size regime (10-50nm). Characterization of the dried or heat-treated samples was carried out using a scanning electron microscope (SEM), nitrogen adsorption and TG-DTA. Depending on not only the initial concentration of PAAm but on the post-gelation treatment on wet-gels, the mesopore structure of dried gels exhibited dramatic change. Solvent exchange by water/ethanol will influence the swelling-deswelling state of PAAm strongly associated with silica, and may have resulted in the final mesopore structure of smaller pore size (3-10nm) and sharper pore size distribution.
9:00 PM - S4.10
Structural and Photoluminescence Features of Eu3+ Based Amorphous and Lamellar Bridged Silsesquioxanes
Sonia Nobre 1 2 , Rute Ferreira 1 , Carole Carcel 2 , Michel Man 2 , Joel Moreau 2 , Luis Carlos 1 Show Abstract
1 Physics and CICECO, University of Aveiro, Aveiro Portugal, 2 Laboratoire Hétérochimie Moléculaire et Macromoléculaire (UMR-CNRS 5076), Ecole Nationale Supérieure de Chimie de Montpellier, Montpellier France
Organo-bridged silsesquioxanes are hybrid materials with potential technological applications owing to the myriad of properties that can be introduced through the organic fragments. Recently, the introduction of urea as self associative groups in the organic fragment and also under the acid-catalysed hydrolytic condensation allowed a good control of the organisation of these solids at various scale lengths [1,2]. Here we report the synthesis, structural and photoluminescence features of a bis- (trialkoxysilylated) organic molecule capable of self-assembly associating urea functional groups and alkylidene chains incorporating the EuCl3.6H2O salt. The fluoride ion catalysed hydrolysis in ethanol in the presence of a stoichiometric amount of water produces a amorphous hybrid while the acid-catalysed hydrolysis in an excess of water gave rise to the formation of crystalline lamellar hybrid material through a self-organisation process. A recent work reports preliminary results on the effects of the self-assembling of the nanobuild blocks (in this case a aromatic ring) on the photoluminescence properties of the hybrids without Eu3+ . The emission in these materials arises from a mixture of components related with the aromatic rings and the urea bridges . Here we will study the lamellar and the amorphous hybrids without and incorporating EuCl3.6H2O in order to understand the effects of the self-assembling of the nanobuild block on the structural and photoluminescence features. The hybrid-to-Eu3+ energy transfer will be also addressed. The materials are fully characterized by X-ray diffraction, infrared and Raman spectroscopies, 29Si and 13C nuclear magnetic resonance, scanning and transmission electron microscopy, elemental analysis and photoluminescence (emission, excitation and time-resolved modes) techniques.References J. J. E. Moreau, L. Vellutini, M.Wong Chi Man, C. Bied, J.-L. Bantignies, P. Dieudonné, and J.-L. Sauvajol, J. Am. Chem. Soc., 123, 7957-7958,2001.  J. J. E. Moreau, B. P. Pichon, M. Wong Chi Man, C. Bied, H. Pritzkow, J-L. Bantignies, P. Dieudonné, J-L. Sauvajol, Angew. Chem. Int. Ed., 43, 203-206, 2004.  L. D. Carlos, R. A. Sá Ferreira, S. S. Nobre, M. Wong Chi Man, J. J. E. Moreau, C. Bied, B. Pichon, Mater. Sci. Forum (Advanced Materials Forum III), 514-516, 118-122, 2006.  L. D. Carlos, R. A. Sá Ferreira, R. N. Pereira, M. Assunção, V. de Zea Bermudez, J. Phys. Chem. B, 108, 14924 -14932, 2004.
9:00 PM - S4.11
Preparation of Ordered Mesoporous Metal Oxides with Crystalline Framewrork by Nano-replication using Ordered Mesoporous Silicas.
Jeong Kuk Shon 1 , Sung Soo Kim 1 , Byung Guk So 1 , Jiae Yu 1 , Hyung Ik Lee 1 , Jin Hoe Kim 1 , Ji Man Kim 1 Show Abstract
1 chemistry, Sungkyunkwan University, Suwon Korea (the Republic of)
9:00 PM - S4.12
Mesostructured Silica Films With Metal Oxide Doped Pore Walls
Nicola Huesing 1 , Joachim Koehler 1 Show Abstract
1 Inorganic Chemistry, Ulm University, Ulm Germany
Since the development of periodically arranged mesoporous silica materials by Kresge and Beck in 1992, the investigation of this new class of materials found an enormous improvement with respect to the variability of the pore size and pore structure. The great research effort in this field resulted in a large variety of different compositions and morphologies, ranging from silica to mixed metal oxides and from powders to monoliths and thin films. A wide field of possible applications, which range from chromatography, catalysis, sensors to optics, is of interest for these materials.The main goal of this work is the preparation of mixed-metal oxide mesostructured films by a combination of evaporation-induced self-assembly and ligand-assisted templating applying the spin-coating technique. The focus lies on Ge-, Ti-, Fe-, Al-oxide modified silica, with M to Si ratios of 1 : 10 and higher. The ligand-assisted templating allows a selective positioning of the metal species in the silica wall which is advantageous for many catalytic applications with respect to activity and efficiency.For the synthesis of these metal doped silica films, a non-ionic polyether-based surfactant (Brij56) was simultaneously used as the structure-directing agent and ligand for the respective metal-alkoxide, such as titanium isopropoxide, germanium isopropoxide, iron ethoxide and aluminum isopropoxide. These modified surfactants were mixed with a prehydrolyzed silica-solution based on tetraethoxysilane and ethanol. To get different pore arrangements the concentration of the surfactant was varied as well as the spin-coating rotation speed as the main control for the film thickness.To characterize the metal-surfactant-complexes, NMR and UV/vis-spectroscopy were used. The final films were characterized by XRD, XPS, nitrogen porosimetry and TEM.
9:00 PM - S4.13
Glycol-Modified Precursors in the Synthesis of Mesoporous, Monodisperse Particles:Synthesis, Characterization and Catalytic Applications
Jasmin Geserick 1 , Nicola Huesing 1 , Katharina Landfester 2 , Renate Rossmanith 2 , Juergen Behm 3 , Yvonne Denkwitz 3 , Ute Kaiser 4 , Ute Hoermann 4 Show Abstract
1 Inorganic Chemistry, Ulm University, Ulm Germany, 2 Organic Chemistry III, Ulm University, Ulm Germany, 3 Physical Chemistry II, Ulm University, Ulm Germany, 4 Electron Microscopy, Ulm University, Ulm Germany
The focus of this work lies on the synthesis of mesoporous, high surface area SiO2- and TiO2-particles employing ethylene glycol modified precursors (EGMS and EGMT, respectively) and their application as catalyst support. Ethylene glycol modified precursors, such as tetrakis(2-hydroxyethyl)orthosilicate (EGMS) as well as bis(2-hydroxyethyl)titanate (EGMT), have distinct advantages in the synthesis of mesoporous materials compared to commercially available tetraalkoxide precursors, since they have proven to be compatible with lyotropic surfactant mesophases and they allow for a processing in purely aqueous conditions. The latter point additionally gives access to the controlled formation of particles by applying the miniemulsion technique.For a typical synthesis protocol, a dilute hydrochloric acid solution containing an amphiphilic molecule (CTAB, Brij56, P123) and the respective precursor was homogenized with a lipophilic solvent (e.g. Isopar M, a mixture of alkanes) using ultrasonics. The resulting droplets act as minireactors in which the cooperative self assembly process of the surfactant and condensable precursor proceeds. The hybrid inorganic-organic particles were either calcined or treated by solvent extraction for a complete template removal. The combination of cooperative self-assembly and miniemulsion processing allowed to obtain monodisperse mesoporous and in some cases even mesostructured particles with high specific surface areas. The samples were characterized by XRD, electron microscopy (REM, TEM) and nitrogen porosimetry. The potential of these materials for catalytic applications was tested in the low temperature CO oxidation reaction, using Au/TiO2 catalysts. The catalysts were prepared by deposition precipitation. Measurements of the CO oxidation kinetics, both in dilute CO:O2 = 1:1 mixtures and in H2-rich gas mixtures (CO:O2:H2 = 1:1:75) indeed show a high Au-normalized activity and a higher stability (lower tendency for deactivation) of the mesoporous TiO2 based catalysts compared to Au/TiO2 catalysts based on commercial TiO2 (P25, Degussa).
9:00 PM - S4.14
Synthesis and Characterization of Hierarchical Porous Gold Materials.
Gregory Nyce 1 , Joel Hayes 1 , Alex Hamza 1 , Joe Satcher, Jr 1 Show Abstract
1 , Lawrence Livermore National Lab, Livermore, California, United States
Hierarchical porous gold materials were prepared using templating and dealloying techniques. Polystyrene Ag/Au core shell particles were prepared by sequential electroless deposition of gold and silver onto polystyrene microspheres. The core shell particles were cast into a monolith and heat treated at 400 C to form hollow Ag/Au alloy spherical shells. Dealloying the Ag/Au shells selectively removes the silver leaving a shell wall comprised of a nanoporous gold network. Combining templating and dealloying techniques, ultra-low density gold monoliths (0.28 mg/cc, 1.5 % relative density) have been prepared.
9:00 PM - S4.15
Mesoporous Carbon Monoliths from Mesophase Pitch for Electrochemical Applications
Philipp Adelhelm 1 , Bernd Smarsly 1 , Yongsheng Hu 2 Show Abstract
1 , Max-Planck-Institute for Colloids and Interfaces, Potsdam Germany, 2 , Max-Planck-Institute for Solid State Research, Stuttgart Germany
Mesoporous carbon is a favorable material for forthcoming technologies such as supercapacitors, high performance electrodes or catalysis. Until now, most mesoporous carbons are powders made by infiltration of porous templates (usually silica) with a carbon precursor, followed by carbonization and removal of silica. Previously used precursors such as furfuryl alcohol lead to a quite amorphous carbon microstructure, while a higher order of the graphene (i.e. the building blocks of such carbons) structure would be advantageous for such applications due to better chemical stability and higher conductivity. Also, the microporosity (pores < 2nm) should be as low as possible, because it traps and immobilizes molecules. Mesophase pitches (MP) are favorable precursors, since they already exhibit a pre-organized graphitic structure before carbonization, but so far porous carbons based on MP usually were powders. By contrast, a monolithic material shows several advantages. For instance, binder gets redundant, which is normally necessary to form an electrode out of carbon powder.We developed a simple replica process using preformed hierarchically porous silica monoliths prepared by the Nakanishi process , infiltrated by MP as carbon precursor, leading to carbon monoliths (cylinders/plates) up to a length of 10 cm with a 3-dimensional network of macro- (1-5 µm) and uniform mesopores (6 nm, BJH). We studied the carbon microstructure in detail by wide-angle X-ray scattering (WAXS), XPS and EELS. A new WAXS-model  was applied to analyze the graphene microstructure of different carbonization temperatures (700°C-2500°C) and its effect on electrochemical properties. Compared to sugar-based precursors, the MP-based carbon microstructure shows a higher order in terms of the graphene size and arrangement. The produced monoliths are mechanically stable and exhibit negligible micropore content (BET surface area of 300 m2/g and a pore volume of 0.4 -0.6 cc/g). High reversible capacity and superior high rate performance were achieved when the material was used as an anode material in rechargeable lithium batteries. For carbon treated at 700 °C, we measured a capacity of 900 mAh/g at a C-Rate of C/5, which is more than 3 times higher than the value for graphite. The material is also stable under faster cycling and shows 145 mA h g-1 at 30C, and 70 mA h g-1 at 60C. This superior rate performance possibly results from the favorable transport advantages of this hierarchically porous structure and the higher ordered carbon microstructure. The high surface area leads to a high electrode/electrolyte contact area, providing a large number of active sites for charge-transfer reactions. The well-interconnected wall structure reduces the solid-state transport lengths for Li diffusion which is assumed to determine the overall rate performance in these nanostructures.  Smarsly et al. Phys. Chem. Chem. Phys. 2006, 8 Ruland, W.; Smarsly, B. J. Appl. Cryst. 2002, 35
9:00 PM - S4.18
Simple Fabrication of Mesoporous Silica with Remarkable High Temperature Stability at Neutral pH and Ambient Conditions from TEOS
David Hess 1 , Radha Vippagunta 2 , James Watkins 2 Show Abstract
1 Chemical Engineering, University of Massachusetts-Amherst, Amherst, Massachusetts, United States, 2 Polymer Science and Engineering, University of Massachusetts-Amherst, Amherst, Massachusetts, United States
Since their discovery mesoporous silicas prepared using cooperative assembly techniques have been the subject of considerable research. These materials are prepared from tetraethylorthosilicate (TEOS) in aqueous media containing structure directing surfactants or block copolymers at extreme pH. Such processesyield well ordered materials, but the synthesis conditions lead to incomplete condensation of the silica network, which results in significant structural contraction upon calcination and limited thermal, hydrothermal and mechanical stability. Here we report a simple synthesis procedure that, surprisingly, yields nearly complete condensation of the silica network (virtually all Q4 linkages) using cysteamine as the catalyst and polyoxyethylene surfactants as the structure directing agents in buffered solution at neutral pH and ambient temperature. The fully condensed silica network has exceptional structural and thermal stability to the mesoporous material.Marine organisms produce highly ordered hierarchal silica structures at ambient conditions through polypeptide-mediated silica condensation within spatially defined regions delimited by a biomacromolecule template. Much work has been directed towards the study of laboratory mimics of these naturally occurring processes. Recently, small molecule bifunctional amines, including cysteamine, were evaluated at neutral pH conditions as small molecule mimics of the natural catalyst systems and shown to be effective for silica condensation.We combine the cysteamine catalyst system with structure-directing block copolymer surfactants at neutral pH and ambient temperature to produce mesoporous silica. For example, the addition of TEOS to a solution of containing cysteamine, citrate buffer (pH 7.2) and 5wt% Brij amphiphilic block copolymer (polyethylene oxide-polyethylene) in de-ionized water yields mesoporous silica. The resulting mesoporous silica powder was analyzed using XRD, TGA, FTIR, TEM, and NMR. The materials exhibited stability under extreme temperature calcinations (up to 800C) in the presence of water. SAXS shows that 1.0% shrinkage upon calcination up to 800C. The virtual absence of shrinkage is attributed to the high degree of silica condensation mediated by the cysteamine catalyst. 29Si NMR analysis supports this observation. Silica linkages in the as-prepared samples are primarily Q4, indicating a fully developed network structure, despite the ambient temperature and neutral pH conditions used for the synthesis.The preparation of fully condensed mesoporous silica at neutral pH and ambient conditions resolves two limiting issues related to the implementation of these materials in a broad range of applications. High thermal, hydrothermal and mechanical stability is often essential for use in catalysis, separations and device applications while neutral synthesis conditions enables the encapsulation of biomolecules or thermally labile therapeutics for drug delivery and sensor applications.
9:00 PM - S4.19
Synthesis and Applications of Nanostrucured Metal Nitride.
Anna Fischer 1 , Frederic Goettmann 1 , Markus Antonietti 1 , Arne Thomas 1 Show Abstract
1 , Max-Placnk-Institute for Colloids and Interfaces, Potsdam Germany
9:00 PM - S4.20
Polymer Composite Reinforced With Nanodiamonds And Clay.
Valery Karbushev 1 , Ivan Konstantinov 1 , Alexander Semakov 1 , Irina Parsamyan 1 , Valery Kulichikhin 1 , Vladimir Popov 2 Show Abstract
1 , A.V.Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences , Moscow Russian Federation, 2 , Moscow Institute of Steel and Alloys , Moscow Russian Federation
Three different polymers have been used as matrices: LC hydroxypropylcellulose (HPC), amorphous polysulfone (PSF) and styrene-acrylonitrile copolymer (SAN). Composites have been prepared on laboratory mixer Minilab (ThermoHaake) and hand-made mixer of rotor-plunger type. For estimation of particles distribution in polymer matrices the optical microscopy and SEM methods were used. For improving mixing quality and exclusion of large aggregates for several batches so-called colloid-deposition method was applied – preparing of mutual suspension of polymer and ND particles in inert liquid medium under action of ultrasound field with further filtration. The average diameter of ND particles visible in optical microscope was around 1-3 mkm. We were wondered to see that shear field increases the tendency of particles to formation of aggregates of different shape in liquid nanocomposite precursors. Presumably, elasticity of matrix and coupling of matrix with particles play important role in aggregation mechanism. Depending on dispersion medium and surfactants we can see in transparent shear cell either radial or ring-like structures formed by NA particles. For clay particles X-ray diffraction method is one of the most informative for estimation of intercalation of polymer molecules to interspaces of clay structure. Since difractograms in two directions are virtually the same (no clay’s reflexes), it is likely that macromolecules not only intercalate clay structure, but can destroy it completely. Measurements of rheological properties of composite melts was performed on rheometer RheoStress RS600 using operating unit plate-plate and capillary viscosimeter of melt-indexer type. The most interesting feature of the viscometrical data consists in non-monotonous location of dependences of viscosity on shear stress, i.e., for non-filled polymer melt the viscosity is not lowest but engages position in the middle of corresponding curves inherent for the filled compositions. The same effect was observed in regime of low-amplitude sinusoidal oscillations: the value of loss modulus for nanocomposite precursors at definite filling degree is less than for neat polymers. The probable explanations of this effect have been considered: formation of absorbed layer by disentangled macromolecules, presence in the system of small gaps where local velocity gradient is much higher than average, specific layered flow mechanism, change of distribution of particles by dimensions in strong shear stream, orientation effects on the level of particles and absorbed layers, preferable absorption of high molecular weight species, etc. Mechanical properties of extruded samples of the circle cross-section were measured on tensile machine Instron 1122. The best performance were realized for formulation containing 0,5 – 1 wt.% of ND. Authors thank for financial support ISTC foundation (project 3238) and Russian Foundation for Basic Research (grants 04-03-32152 and 05-03-08028).
9:00 PM - S4.21
Modification of Nanocomposites/Hybrid Organic-Inorganic Porous Clay Heterostructures for Ethylene Scavenger in Packaging Film
Kasinee Prakobna 1 , Rathanawan Magaraphan 1 , Hathaikarn Manuspiya 1 Show Abstract
1 The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok Thailand
Recently, the discovery of a new class of solid porous materials known as porous clay heterostructures (PCH) has been reported. These materials have been prepared by the surfactant-directed assembly of mesostructures silica within the two-dimensional interlayer spacing of clays. The PCH is interesting material to use as entrapping system owing to its structure provides high surface area with uniform and specific pore size. In this work, the PCH is synthesized within the galleries of Na-bentonite clay by the polymerization of tetraethoxysilane (TEOS) in the presence of surfactant micelles (cetyltrimethylammonium bromide and dodecylamine). In addition, a mesoporous clay with hybrid organic-inorganic PCH (HPCH) is modified via co-condensation reaction of TEOS and methyltriethoxysilane (MTS) resulting in the incorporation of methyl group. The effect of pH on the formation of these mesoporous structures was investigated by adjusting pH of Na-bentonite clay to pH 9, 7, 5 and 3 before the modification and then observed the effect of pH by using N2 adsorption-desorption technique. The results shown that the PCHs and HPCHs had surface areas of 501-668 and 467-582 m2/g, pore volume of 0.47-0.58 and 0.33-0.49 cc/g, and average pore sizes in the small mesopore to supermicropore range of 3.01-3.85 and 1.37-3.88 nm, respectively. Furthermore, both PCHs and HPCHs are utilized as ethylene scavenger and blended with polypropylene for producing ethylene scavenging films in food packaging application. In this work, the direct melt intercalation method was applied to prepare the nanocomposites pellets by mixing 1 wt% of porous clay materials, 2 wt% of surlyn ionomer acting as a compatibilizer, and polypropylene under shear and further prepare thin film nanocomposites via blow film extrusion. The eight samples of nanocomposites films including PCH-9, 7, 5, 3 and HPCH-9, 7, 5, 3 (numerals denote the pH-adjusted condition of Na-bentonite clay) will be measured oxygen and ethylene permeabilities; however, the present results obtained from PCH-9 and HPCH-9 nanocomposites films revealed that the PCHs and HPCHs nanocomposites had oxygen permeability rate of 581.48 and 482.04 cm3/m2.d.atm, respectively, which reduced from oxygen permeability rate of polypropylene film (609.42 cm3/m2.d.atm). In addition, ethylene permeability rate of PCHs and HPCHs nanocomposites were 517.41 and 488.90 cm3/m2.d.atm, respectively, which also reduced from ethylene permeability rate of polypropylene film (537.37 cm3/m2.d.atm). It seems that both PCH and HPCH materials affect gas barrier properties of the nanocomposites films and the HPCH could improve gas barrier properties than the PCH because the HPCH has more hydrophobicity in consequence of incorporating with methyl group. So the HPCH material provide more interaction with ethylene gas resulting in improvement in ethylene barrier property and also improve oxygen barrier property because its pore size less than PCH material.
9:00 PM - S4.22
Synthesis and Characterization of MoS2 Intercalated with 1,2,3,4 Tetrahydroquinoline in Search of Cleaner Fuels.
Karina Castillo 1 , Russell Chianelli 1 , Jason Parsons 1 , Felicia Manciu 1 Show Abstract
1 , University of Texas at El Paso, El Paso, Texas, United States
9:00 PM - S4.23
Microstructure, Composition and Functional Properties of Organosilicon Plasma Polymers.
Lenka Zajickova 1 , Bursikova Vilma 1 , Zuzana Kucerova 1 , Pavel Stahel 1 , Dan Franta 1 , Vratislav Perina 2 , Anna Mackova 2 Show Abstract
1 Deptartment of Physical Electronics, Masaryk University, Brno Czech Republic, 2 , Institute of Nuclear Physics, Rez Czech Republic
9:00 PM - S4.24
Organic-inorganic hybrid materirals using cubic-silsesquioxane as nano-building block.
Ken-ichi Shinotani 1 , Norihiro Takamura 1 , Richard Laine 2 Show Abstract
1 , Matsushita Electric Works, Ltd., Kadoma Japan, 2 Macromolecular Science and Engineering, University of Michigan, Ann Arbor, Michigan, United States
Feasibility study for applying cubic-silsesquioxane hybrid to electronic as well as optical material has been conducted. With regards to the electronic material application, cubic-silsesquioxane/epoxy hybrid system was investigated, while for the optical material application, caged-silsesquioxane hydro-silylation system was examined.The octa-amino phenyl cubic silsesquioxane(OA) was utilized as a nano-building block for the epoxy hybrid system. The OA was cross-linked by epoxy resin(@180C) to provide hybrid resin plate and then the cured hybrid properties as electric materials(glass transition temperature, CTE, )are examined.By changing the structure of epoxy resin, the relationship between epoxy structure and cured hybrid properties is investigated. The tetrakis(cyclohexenylethyldimethylsiloxy)octa-silsesquioxane(TCHS) was choose as nano building block for the hydro-silylation hybrid system. The self-cross linked TCHS resin plate(@200C) were subjected to the optical property measurement such as UV-vis along with durability for UV light(@380nm) exposure test. Small angle X-ray scattering measurement was conducted on the TCHS resin plate in order to clarify the network structure of the hybrid in comparison to the epoxy resin plate. Epoxy hybrid resin that cross-linked with OA and DGEBA(eq=170), indicated very high thermal stability and elimination of glass transition was observed, while the hybrid cross-linked by the epoxies that possess longer chain(DGEBA eq=650) as well as Bromine atom substituted showed the glass transition. On the other hands, the dielectric constant of resin plate of OA/DGEBA(eq=170) were much higher than the OA/DGEBA(eq=650) and OA/Br-DGEBA. These results are attributed to the network structure of hybrid materials that was formed by interconnection between cubic silsesquioxane nano block and epoxy resin was discussed. The CCL(Copper clad laminate) was fabricated by the hybrid system and the elimination of Tg as well as good enough flame retardancy of laminate with much lower bromine content % was clarified. Through these study, we clarify the feasibility of the hybrid to apply it for electric material usage. TCHS hybrid resin showed very high transparency even in an exposure of short wave length light.The transmittance of short wave length range light is much better than a transparent epoxy resin system such as aliphatic epoxy rein and is identical with that of inorganic glass material. The TCHS also indicated very high durability for exposure of UV(@380nm) light. Thus the hybrid possesses the advantage of inorganic glass materials while keeping an advantage of organic resin such as low temperature low cost process. This allows us to consider the hybrid system application for the optical devices that is operating using short wavelength light.
9:00 PM - S4.25
A New Fabrication Method of Organic-Inorganic Hybrid Thin Films Using Molecular Layer Depostion
Byoung Hoon Lee 1 , Kyo Keun Im 1 , Myung Mo Sung 1 Show Abstract
1 Chemistry, Hanyang University, Seoul Korea (the Republic of)
Organic-inorganic hybrid films were fabricated by a new growth technique that can control thickness with nanometer level. This method is based on molecular layer deposition of self-assembled monolayers (SAMs) in gas phase. The alkene terminated alkysiloxane self-assembled monolayer was formed by exposing a substrate to C=C terminated alkyltrichlorosilane and water vapor in ALD chamber. The terminal vinyl groups were converted to carboxylic groups with ozone treatment. The highly active titanium hydroxyl linker layer was formed on the carboxylic terminated SAMs by using titanium isoproxide adsorption followed by exchange reaction of water molecule in order to provide highly active adsorption sites for the anchoring of the next monolayer. The hybrid films, which are sequentially deposited in ALD chamber, were investigated by using x-ray photoelectron microscopy (XPS), contact angle analysis (CAA), atomic force microscopy (AFM), transmission electron microscopy (TEM) and digital multi-meter.
9:00 PM - S4.26
Sensitive-dye incorporated PP/Clay Nanocomposites
Sakkarin Tassanawat 1 , Minit Nithitanakul 1 , Rathanawan Magaraphan 1 , Hathaikarn Manuspiya 1 Show Abstract
1 Petroleum and Petrochemical College, Chulalongkorn University, Bangkok Thailand
The color indicator for fresh milk packaging has been newly developed to evaluate the degree of fresh milk deterioration during storage and distribution. The processing of pH-sensitive material used for milk packaging based on organomodified clay nanocomposites incorporated with indicator dye was focused. The nanoclay composites with indicator dye were melt compounding through a twin screw extruder by using Surlyn® as a reactive compatibilizer. The nanoclay composites were fabricated into the sample sheet for Hunter color test. Milk deterioration was assessed for titratable acidity (TA), and color changes of the indicator were measured and expressed as Hunter values as well as total color difference (TCD). TCD values of bromothymol blue (BMB) type indicator (containing BMB as a chemical dye) also changed continuously with the response of the indicator. The color changes of the indicator correlated well with TA value of fresh milk. According to the changes in Hunter color values of the indicator within the packages of fresh milk during storage at room temperature, Hunter L and b values increased gradually with storage time, while Hunter a decreased slowly. The result means that the color of BMB type indicator turned from initially bluish-green to finally yellow. The color changes of the developed indicator represented properly the degree of deterioration of fresh milk. The pH indicator could be employed an effective smart packaging technology for evaluating fresh milk.
9:00 PM - S4.27
Characteristics of SiCN Microstructures Fabricated by Using PDMS Molds
Gwiy Chung 1 , Ki-Bong Han 1 Show Abstract
1 School of Electrical Enginnering, University of Ulsan, Ulsan Korea (the Republic of)
This paper describes a novel fabrication process of high-temperature MEMS based on liquid-polysilazane-derived SiCN ceramic microstructures. First, PDMS (polydimethylsiloxane) molds were fabricated on SU-8 photoresist using standard UV-photolithographic process. Liquid polysilazane (Kion Corp., VL 20) and photoinitiator (2,2-dimethoxy-2- phenyl acetophenone) were injected into the PDMS mold. The liquid-phase polysilazane is converted into solid-phase polysilazane by UV exposure. And then, solid-phase polysilazane structure is cross-linked using HIP (hot isostatic press) at 400°C, 205 bar. Thermal decomposition transformed the polymer to a ceramic capable of withstanding over 1400°C. In addition, Physical and electric properties of SiCN microstructure with different pyrolysis conditions were evaluated. The SiCN microstructures, which is pyrolyzed at HIP, have the greatest insulation resistance and break down voltage characteristics than other SiCN samples or Si substrate. Finally, Optimum pyrolysis process condition was determined for SiCN microstructure fabrication. Consequently, the fabricated SiCN ceramic microstructures may be applied for high-temperature and high-power MEMS applications, such as heat exchanger and combustion chamber.
9:00 PM - S4.28
Synthesis and Properties of Molecular Sub-structures of the Silicon Crystal Lattice.
Andreas Wallner 1 , Jelena Fischer 1 , Judith Baumgartner 1 , Christoph Marschner 1 Show Abstract
1 Institut für Anorganische Chemie, TU Graz, Graz Austria
9:00 PM - S4.29
Hybrid Organic-Inorganic Sol-Gels with A Cleavable Tetrasulfide Bridging Group.
Guangqing Guo 1 , Douglas Loy 1 , Dylan Boday 1 Show Abstract
1 Materials Science and Engineering, University of Arizona, Tucson, Arizona, United States
Thiol-functionalized hybrid materials have attracted much attention in recent years due to their many potential applications for metal ion adsorption, separation, and metallic nanoparticles stabilization. Thiol-functionalized materials were prepared either by grafting mercaptopropyltrialkoxysilane onto pore surface of mesoporous silica, or by co-polymerization of mercaptopropyltrialkoxysilane with tetraethylorthosilicate in the presence of templates. However, both of them have their own limitations, such as bad distribution and low content of thiol group in the materials. Here, we describe a new procedure to prepare thiol-functionalized polysilsesquioxanes using a post-processing modification method. This approach involves a copolymerization of phenylene-bridged monomer and tetrasulfide-bridged monomer followed by reductive cleavage of tetrasulfide to thiols under very mild conditions. Because each tetrasulfide can generate two thiols, the technique allows the introduction of relatively high level of functionality for capturing metal ions. In this study we have prepared materials using standard sol-gel polymerization techniques and with surfactant templating. Results of their characterization and performance as platinum scavengers will be presented.
9:00 PM - S4.3
Phase Separation in Al2O3 Sol-gel System Incorporated With High Molecular Weight Poly(ethylene oxide).
Yasuaki Tokudome 1 , Kazuki Nakanishi 2 , Koji Fujita 1 , Kiyotaka Miura 1 , Kazuyuki Hirao 1 Show Abstract
1 , Graduate School of Engineering, Kyoto University, Kyoto Japan, 2 , Graduate School of Science, Kyoto University, kyoto Japan
Polycrystalline alumina (Al2O3) and aluminate ceramics have a broad range of application owing mainly to their high mechanical stability. Porous alumina/aluminates as well as the silicate families have been widely used as catalyst supports. It has been reported that monolithic silica, siloxane-based hybrid and titania materials with well-controlled hierarchical pore systems can be synthesized via sol-gel route accompanied by phase separation. Sol-gel alumina/aluminates, however, have rarely been prepared in monolithic form, because of the difficulty in controlling the reactivity of the precursors. Starting from aluminum salts, Gash et al. reported that monolithic alumina gels, together with supercritically dried aerogels, can be prepared.In our experiments, pure alumina monoliths with well-defined macropores and mesostructured skeleton have been synthesized via a spontaneous route from the aqueous and ethanolic solution of aluminum salts in the presence of propylene oxide and poly(ethylene oxide)(PEO). The addition of propylene oxide to the starting solution controls the gelation, while the addition of PEO induces the phase separation. Adequate choice of the starting composition, by which the phase separation and gelation concur, produces large-dimension (10mm×10mm×10mm), bicontinuous macroporous Al2O3 monoliths. The size of macropores is controlled in the range of 400 nm to 1.8 μm, depending on the starting composition. The dried gel is amorphous, while the heating at temperatures above 800 οC for 5 h leads to the formation of crystalline phases without spoiling the macroporous morphology; nanocrystalline γ-Al2O3 is precipitated at 800 οC, α-Al2O3 starts to form at 1000 οC in addition to γ-Al2O3, and complete transformation of γ-Al2O3 into α-Al2O3, i.e., the formation of a single phase of α-Al2O3, is achieved at 1100 οC. Nitrogen adsorption-desorption measurements revealed that the skeletons of dried gels possess the mesostructure with a median pore size of about 2.6 nm and with the surface area as high as 300~400 m2/g.
9:00 PM - S4.30
Inorganic Organic Composite Polymer Coatings Based on Functionalised Polyhedral Oligomeric Silsesquioxanes.
Duncan Robertson 1 , Russell Morris 1 Show Abstract
1 Chemistry, University of St Andrews, St Andrews, Fife, United Kingdom
9:00 PM - S4.31
An Organic-inorganic Hybrid Polymeric Nanocomposites for the Hard Coat Application on Flat Panel Displays.
Raymond Tsiang 1 , Hau-Chun Chiang 1 Show Abstract
1 Chemical Engineering, National Chung Cheng University, Ming-Hsiung, Chiayi Taiwan
9:00 PM - S4.32
Templating of Hybrid Cationic Inorganic 2D Materials using Interlamellar Organic Anion Arrays
David Rogow 1 , Claudia Swanson 1 , Xiaojuan Fan 1 , Scott Oliver 1 Show Abstract
1 Chemistry and Biochemistry, University of California Santa Cruz, Santa Cruz, California, United States
We are investigating the solvothermal synthesis of new inorganic materials using organic small molecule templates. We have discovered a series of 2D cationic inorganic layered structure types using different carbon chain length alkyldisulfonate molecules. The organic molecules form a surfactant assembly, directing the structure and charge of the inorganic framework. Unlike existing 2D hybrid inorganic-organic materials, our examples are the only synthetic examples where the inorganic portion is cationic and the anionic portion is organic. The only known cationic layered structures that can exchange their anions are the layered double hydroxides (LDHs). All of the LDHs are isostructural, whereas our structures do not exhibit the same coordination and geometry around the metals as well as having different bridging atoms. These types of materials may be useful for intercalation of anions in a number of applications including base catalysis and anion exchange.
9:00 PM - S4.33
Tuning of Glass Transition in Nanoparticle-embedded Polymers through Contolled Variation of Interfacial Morphology
Jaydeep Basu 1 , Sunita Srivastava 1 Show Abstract
1 Physics, Indian Institute of Science, Bangalore, Karnataka, India
9:00 PM - S4.34
Chemical Raction of Hydrogenated Diamond Surface with Amino Acid in Solvent Containing Radical Initiator.
Toshiki Tsubota 1 , Yuta Hagiwara 1 , Teruhisa Ohno 1 Show Abstract
1 Department of Chemistry, Faculty of Engineering, Kyushu Institute ofTechnology, Kitakyushu, Fukuoka, Japan
9:00 PM - S4.35
Nanostructured Ceramic or Hybrid Thin Film and Coating Process thereof for Silica and Zirconia Based-materials.
Valle Karine 1 , Guenadou David 1 , Belleville Philippe 1 , Bianchi Luc 1 , Wittmann-Teneze Karine 1 , Boscher Christophe 1 Show Abstract
1 , CEA, Monts France
9:00 PM - S4.36
Studies on Photoluminescence from Porous Silicon by Post Anodization Treatment in MEH-PPV.
Pallab Banerji 1 , Susanta Banerjee 1 , Jayanta Mishra 1 Show Abstract
1 Materials Science Centre, Indian Institute of Technology, Kharagpur India
9:00 PM - S4.38
New Organo-inorganic Materials for Water Contaminants Remediation.
Aracely Ortiz 1 , Rosa Richards 1 , Elena Otazo 1 , Otilio Acevedo 1 , Francisco Prieto 1 , Juan Hernandez 1 , Alberto Gordillo 1 Show Abstract
1 Centro de Investigaciones Quimicas, Universidad Autonoma del Estado de Hidalgo, Pachuca, Hidalgo, Mexico
9:00 PM - S4.4
Comparison of Different Reversed-Phase Packing Materials Based on Higher Organic Hybrid Particles.
Nicole Lawrence 1 , Kevin Wyndham 1 , Ken Glose 1 , Jim Cook 1 , Darryl Brousmiche 1 , Pamela Iraneta 1 , Bonnie Alden 1 , Cheryl Boissel 1 , Thomas Walter 1 Show Abstract
1 , Waters Corporation, Milford, Massachusetts, United States
9:00 PM - S4.41
Low Temperature Deposition of Metal Oxide Thin Films in Supercritical Carbon Dioxide using Metal-organic Precursors.
Theodosia Gougousi 1 , Zhiying Chen 1 Show Abstract
1 Physics, UMBC, Baltimore , Maryland, United States
9:00 PM - S4.42
Effect of Particle Morphology and Interfacial Behavior on Properties of Hydroxyapatite Nanocomposites.
Jasmeet Kaur 1 , Meisha Shofner 1 Show Abstract
1 School of Polymer, Textile and Fiber Engineering, Georgia Institute of Technology, Atlanta, Georgia, United States
9:00 PM - S4.43
Constitutive Response of Collagen Hydrogels Around a Sharp Notch Under Tension
Joshua Lee 1 , Michael Shaw 1 Show Abstract
1 Bioengineering, California Lutheran University, Thousand Oaks, California, United States
Wounds that penetrate multiple dermal layers in human skin trigger cellular signaling cascades that initiate healing and reconstructive processes. Specifically, in addition to biochemical cues, cells both induce and respond to mechanical signals through a variety of mechanotransduction processes. These mechanical cues may originate directly from the extracellular matrix (ECM) or from neighboring cells within the ECM. Prior studies have correlated tensile stress and strain with a variety of cell responses, including development of scar tissue. However, although the redistribution of strain and stress around sharp notches are known for linear elastic and strain-hardening materials, this information has yet to be established for hyperelastic materials. Such materials include those envisaged as skin replacement scaffolds, specifically collagen and fibrin hydrogels. Hybrid scaffolds created through the inclusion of stiff, second phase particulates, such as calcium phosphate and hydroxyapatite particles are also candidates for treating bone defects. This knowledge is critical for the design of skin replacement materials for controlled, scarless healing, especially in the vicinity of incisions, sutures and other structural discontinuities.Here, we utilize a novel, in situ notched-tensile specimen to determine the magnitude and distribution of in-plane strain in the region of the notch-tip in a Type-I collagen specimen. Experiments were performed with model specimens in-situ using a fixture mounted on the stage of an optical microscope. A scalpel was used to give a full-thickness notch through the center of each specimen and inert, image-contrasting markers were applied to the surface of the specimen in the notch tip region. A remote, tensile strain was applied in a step-wise linear fashion and multiple high-resolution images collected at different levels of far-field strain. Image analysis was then performed using a coordinate system to track movements of individual markers from a series of sequential images. The resultant displacement fields were then analyzed to yield the in-plane strain fields, including in-plane strain components along trajectories parallel and perpendicular to the crack plane.Significant local strain concentrations were observed near the notch tip of well over 180% within a region extending to nearly 1 mm from the notch tip. Regions of over 20% strain elevation were also observed at distances of up to 2.5 mm from the notch tip. The magnitudes and spatial dependence of these strain concentrations are then analyzed using known constitutive models for crack-tip strain fields in linear elastic and strain-hardening materials. Furthermore, the results are interpreted with respect to previous studies correlating magnitudes of strain and cell function. Finally, implications for the design of skin replacement scaffolds and bone replacement hybrid scaffolds are presented.
9:00 PM - S4.44
Preparation and Properties of Amino-Terminated Anionic Waterborne Polyurethane-Silica Hybrid Materials through Sol-Gel Process in the Absence of External Catalyst
Jui-Ming Yeh 1 Show Abstract
1 Chemistry, Chung Yuan Christian University, Chung Li Taiwan
In this paper, a series of polymer-silica hybrid materials consisted of amino-terminated anionic waterborne polyurethane (WPU) and inorganic silica particles have been successfully prepared through the sol-gel process in the absence of external catalyst. Typically, amino-terminated anionic WPU was first synthesized from specific feeding molar ratio of polycaprolactone (PCL), dimethyllo propionic acid (DMPA) and 4,4'-methylenebis(cyclohexylisocyanate) (H12MDI), followed by further reacting with TEA and TETA to give as-prepared WPU. The obtained WPU was characterized by FTIR spectroscopy and gel permeation chromatography (GPC). Subsequently, a series of hybrid materials with different silica content were prepared by performing the sol-gel reactions of tetraethyl orthosilicate (TEOS) in the amino-terminated WPU matrix without the addition of external catalyst and followed by examined by transmission electron microscopy (TEM), powder XRD, solid-state NMR and FTIR. It should be noted that the terminated primary amine groups attached on the as-prepared WPU chains could be functioned as internal base catalyst for the sol-gel process of TEOS. Effect of material composition on the thermal stability, mechanical strength, surface wettability and optical clarity of hybrid materials was also evaluated by the TGA, DMA, contact-angle measurement and UV-vis transmission spectroscopy, respectively.
9:00 PM - S4.45
Study on the Adsorption Behavior of Fluorescence Protein in the Pure and Modified clays
Tsung-Yen Tsai 1 , Yun-Zhen Tseng 1 Show Abstract
1 Chemistry, Chung Yuan Christian University, Chung-Li Taiwan
In order to purify the fluorescence protein for further application in the biosensors, we apply nanolayer materials as an adsorption subtract. In this study, when clays were intercalated by cocamidopropylhydroxysultaine, the adsorption of DsRed protein (Red fluorescence protein) could be improved for modified clays. The enhancement of the adsorption of DsRed protein was influenced by the kind of diluted water, pH condition of modified clay, and the concentration of the protein. The optimized process conditions of the protein adsorption has shown when the protein was intercalated/adsorbed by the modified clay, pretreated with cocamidopropylhydroxysultaine (C-50) in RO water with pH=7~8. The intercalation/adsorption amount of the protein was highly increased from 0.1083 mg/ml to 0.3448 mg/ml when the purified clay was treated by C-50, compared with the purified clay. This result shows that the protein, DsRed, was successfully intercalated/ adsorbed in the gallery of clay. There were evidences made by XRD, TGA and FTIR analysis.
9:00 PM - S4.46
Nanoscale Toughness of Ductile Materials Using Nanoindentation
Jiahau Yan 1 , Burak Taskonak 1 Show Abstract
1 Restorative Dentistry, Indiana University , Indianapolis, Indiana, United States
One of the main reasons for constructing nanosized organic/inorganic hybrid materials is to achieve high toughness. However, to date, there is no established method for measuring the toughness of ductile materials at nanoscale. While the toughness of brittle materials at nanoscale can be characterized using crack length and a fracture mechanics method similar to that of microindentation, it cannot be applied to estimate the toughness of ductile materials since generally no cracks are formed during the indentation process. We propose using a nanoindentation technique to measure the toughness of ductile materials based on the energy consumed in the plastic deformation regime and the volume created by the indents. We performed nanoindentation on soda-lime glass, gold, and poly-methyl methacrylate (PMMA) using a maximum load of 36 mN. The plastic energy was calculated from the plastic part of load-displacement curves. The volumes of the indents were estimated from scanning images and depth profiles. The toughness was then calculated using the plastic energy divided by the indent volume. The toughness values of glass, gold, and PMMA were 3.3x10^7, 1.3x10^9, and 3.1x10^9 J/m^3, respectively. It was found that the toughness of gold is 94 times that of glass and 2.4 times that of PMMA. The load-displacement curves of glass, gold, and PMMA shows different plasticity for the three materials. The plastic regime and toughness of gold and PMMA are much great than that of glass. We suggest that this method can be applied to study the toughness of biological composites or organic/inorganic hybrid materials at nanoscale.
9:00 PM - S4.49
3D Composites Based on Hydroxyapatite-Chitosan-Polysiloxane as a Biomimetic Scaffold Materials.
Andronico Carrillo 1 , Jose Arias 1 , Soledad Fernandez 1 , Claudia Quilodran 1 , Jose Arias 1 Show Abstract
1 CIMAT, Biological and Animal science, University of Chile, Santiago Chile
9:00 PM - S4.5
Mesostructured Materials Containing [Re6Q8(CN)6]4- Cluster Anion
MinJung Suh 1 , Sung Huh 1 , Vien Vo 1 , Youngmee Kim 1 , Sung-Jin Kim 1 Show Abstract
1 NanoScience, Ewha Womans University, Seoul Korea (the Republic of)
We synthesized the new mesostructured materials by a surfactant-templated assembly of [Re6Q8(CN)6]4-(Q= Te, Se), an octahedral cluster precursor. The mesostructured lamellar phases with the general formula [CnH2n+1N(CH3)3]4[Re6Q8(CN)6] (n=14,16,18) (Q= Te, Se) were prepared by ion exchange/precipitation reaction of alkyltrimethylammonium surfactants and the cluster K4[Re6Q8(CN)6] in H2O/acetone medium at room temperature. The rhenium clusters in the lamellar material were charge balanced by surfactants. The other mesostructured cubic phases materials were synthesized by the assembly of hexanuclear rhenium chalcocyanide cluster, TMA4[Re6Se8(CN)6], and transition metal cations(Co2+, Mn2+) in formamide at 60 degrees. The transition metal ions linked rhenium cluster to rhenium cluster. The two phases were characterized using powder X-ray diffraction, single-crystal X-ray diffraction ([C14H29N(CH3)3]4[Re6Te8(CN)6], [C16H33N(CH3)3]4[Re6Se8(CN)6]), IR spectroscopy, Raman spectroscopy, TEM, thermogravimetric and differential scanning calorimetry means. The crystal data of [C14H29N(CH3)3]4[Re6Te8(CN)6] are a=11.4818(50) Å, b=11.6253(48) Å, c=22.2004(97) Å, α= 78.24(1) °, β= 82.31(1) °, γ= 61.28(1) °, triclinic, space group = P-1, and Z=1. The crystal data of [C16H33N(CH3)3]4[Re6Se8(CN)6] are a=11.7167(50) Å, b=11.8438(37) Å, c=21.3933(97) Å, α= 87.996(21) °, β= 87.5891(18) °, γ= 60.972(23) °, monoclinic.
9:00 PM - S4.50
Conducting Adhesives for Advanced Manufacturing
Douglas Schulz 1 , Kristen Keller 1 , Samali Datta 1 2 , Dean Webster 1 2 Show Abstract
1 Center for Nanoscale Science and Engineering, North Dakota State University, Fargo, North Dakota, United States, 2 Department of Coatings and Polymeric Materials, North Dakota State University, Fargo, North Dakota, United States
Conventional silver paste inks contain considerable solvent, which contributes to air pollution. UV curable technology can eliminate or minimize the solvent content; however, current commercial UV curable inks have poor conductivity and cannot be thermally bonded to another material (i.e. an antenna). UV "curable" inks having improved conductivity and maintain thermoplasticity were prepared and optimized for screen printing and other key properties. Screen printed deposits on FR-4 boards showed dc sheet resistance 0.074 Ω/sq/mil and ac impedance (6.0 GHz) of 466 µdB/mil as compared to 0.017 and 299 for a Cu control, respectively. The applicability of these materials (and similar variants) in the manufacture of large-area electronics (e.g., rfid tags) will be discussed.
9:00 PM - S4.6
New Generation of Hybrid Organic-Inorganic macrocellular Foams: Integrative Chemistry toward Reaching Enhanced Heterogeneous Catalysis and Scavenging Properties
Ungureanu Simona 1 3 4 , Herve Deleuze 4 , Clement Sanchez 2 , Marcel Popa 3 , Renal Backov 1 Show Abstract
1 , CNRS-Universite Bordeaux-I, Pessac France, 3 , Facultea Chimie Industriala, Iasi Romania, 4 , Université Bordeaux-I, Iasi France, 2 , CNRS-Université Pierre et Marie Curie, Paris France
9:00 PM - S4.7
The Solvent Effects on the Formations of Lanthanide-Organic Porous Frameworks
Kuei-Fang Hsu 1 Show Abstract
1 Chemistry, National Cheng Kung University, Tainan Taiwan
The utilization of various solvents in the similar hydrothermal reactions has obtained two new lanthanide-based organic hybrid materials. Crystal Data: 1, Orthorhombic Fddd, a = 9.7277(4) Å, b = 15.4399(6) Å, c = 28.0108(12) Å, Z = 8, V = 4218.5(5) Å3; 2, Monoclinic P21/c, a = 6.3295(3) Å, b = 9.4446(5) Å, c = 16.1768(8) Å, b = 93.283(1)o, Z = 2, V = 965.5(2) Å3. Both structures are composed of neodymium ions, oxalates ligands and succinates ligands to form the porous frameworks with multi-dimensional tunnels. In 1, the Nd3+ ions are coordinated with four succinates and one oxalate- in the geometry of distorted square-pyramidal; while in 2, the Nd3+ ions are coordinated with four oxalates and one succinate in the geometry of distorted trigonal-bipyramidal. Both frameworks can be viewed as two-dimensional nets pillared by the oxalate ligands. The thermal stability and antiferromagnetic behaviors of the two compounds will be presented.
9:00 PM - S4.8
Preparation of Polyaniline Nanowires in Porous Alumina Templates.
Jinsub Choi 1 , Kyungja Kim 2 1 , Sung Joong Kim 1 , Jeong Ho Chang 1 Show Abstract
1 Nanomaterials Application Division , Korea Institute of Ceramic Engineering and Technology (KICET), Seoul Korea (the Republic of), 2 Department of Electrical and Computer Engineering , University of Illinois at Urbana-Champaign, Urbana, Illinois, United States
9:00 PM - S4.9
synthesis of Various Ordered Mesoporous Carbons with Controlled Properties and its Application as Catalyst Support of Dirct Methanol Fuel Cell.
Hyung Ik Lee 1 , Jin Hoe Kim 1 , Chanho Pak 2 , Sang Hoon Joo 2 , Hyuk Chang 2 , Doyoung Seung 2 , Ji Man Kim 1 Show Abstract
1 chemistry, Sungkyunkwan University, Suwon Korea (the Republic of), 2 , Samsung Advanced Institute of Technology, SAIT, Suwon Korea (the Republic of)